Occurrence, Fate and Impact of Atmospheric Pollutants on Environmental Health 0841228906, 9780841228900, 9780841228917

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Publication Date (Web): November 8, 2013 | doi: 10.1021/bk-2013-1149.fw001

Occurrence, Fate and Impact of Atmospheric Pollutants on Environmental and Human Health

In Occurrence, Fate and Impact of Atmospheric Pollutants on Environmental and Human Health; McConnell, L., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013.

Publication Date (Web): November 8, 2013 | doi: 10.1021/bk-2013-1149.fw001 In Occurrence, Fate and Impact of Atmospheric Pollutants on Environmental and Human Health; McConnell, L., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013.

ACS SYMPOSIUM SERIES 1149

Publication Date (Web): November 8, 2013 | doi: 10.1021/bk-2013-1149.fw001

Occurrence, Fate and Impact of Atmospheric Pollutants on Environmental and Human Health Laura L. McConnell, Editor USDA-ARS Beltsville, Maryland, United States

Jordi Dachs, Editor Institute of Environmental Assessment and Water Research Barcelona, Spain

Cathleen J. Hapeman, Editor USDA-ARS Beltsville, Maryland, United States

Sponsored by the ACS Division of Agrochemicals

American Chemical Society, Washington, DC Distributed in print by Oxford University Press

In Occurrence, Fate and Impact of Atmospheric Pollutants on Environmental and Human Health; McConnell, L., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013.

Publication Date (Web): November 8, 2013 | doi: 10.1021/bk-2013-1149.fw001

Library of Congress Cataloging-in-Publication Data Occurrence, fate and impact of atmospheric pollutants on environmental and human health / Laura L. McConnell, editor, USDA-ARS, Beltsville, Maryland, United States, Jordi Dachs, editor, Institute of Environmental Assessment and Water Research Barcelona, Spain, Cathleen J. Hapeman, editor, USDA-ARS, Beltsville, Maryland, United States ; sponsored by the ACS Division of Agrochemicals. pages cm. -- (ACS symposium series ; 1149) Includes bibliographical references and index. ISBN 978-0-8412-2890-0 1. Air--Pollution. 2. Air--Pollution--Health aspects. 3. Human beings--Effect of environment on. 4. Environmental chemistry. I. McConnell, Laura L. II. Dachs, Jordi. III. Hapeman, Cathleen J. IV. American Chemical Society. Division of Agrochemicals. RA576.O33 2013 363.739'2--dc23 2013039376

The paper used in this publication meets the minimum requirements of American National Standard for Information Sciences—Permanence of Paper for Printed Library Materials, ANSI Z39.48n1984. Copyright © 2013 American Chemical Society Distributed in print by Oxford University Press All Rights Reserved. Reprographic copying beyond that permitted by Sections 107 or 108 of the U.S. Copyright Act is allowed for internal use only, provided that a per-chapter fee of $40.25 plus $0.75 per page is paid to the Copyright Clearance Center, Inc., 222 Rosewood Drive, Danvers, MA 01923, USA. Republication or reproduction for sale of pages in this book is permitted only under license from ACS. Direct these and other permission requests to ACS Copyright Office, Publications Division, 1155 16th Street, N.W., Washington, DC 20036. The citation of trade names and/or names of manufacturers in this publication is not to be construed as an endorsement or as approval by ACS of the commercial products or services referenced herein; nor should the mere reference herein to any drawing, specification, chemical process, or other data be regarded as a license or as a conveyance of any right or permission to the holder, reader, or any other person or corporation, to manufacture, reproduce, use, or sell any patented invention or copyrighted work that may in any way be related thereto. Registered names, trademarks, etc., used in this publication, even without specific indication thereof, are not to be considered unprotected by law. PRINTED IN THE UNITED STATES OF AMERICA In Occurrence, Fate and Impact of Atmospheric Pollutants on Environmental and Human Health; McConnell, L., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013.

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Foreword The ACS Symposium Series was first published in 1974 to provide a mechanism for publishing symposia quickly in book form. The purpose of the series is to publish timely, comprehensive books developed from the ACS sponsored symposia based on current scientific research. Occasionally, books are developed from symposia sponsored by other organizations when the topic is of keen interest to the chemistry audience. Before agreeing to publish a book, the proposed table of contents is reviewed for appropriate and comprehensive coverage and for interest to the audience. Some papers may be excluded to better focus the book; others may be added to provide comprehensiveness. When appropriate, overview or introductory chapters are added. Drafts of chapters are peer-reviewed prior to final acceptance or rejection, and manuscripts are prepared in camera-ready format. As a rule, only original research papers and original review papers are included in the volumes. Verbatim reproductions of previous published papers are not accepted.

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In Occurrence, Fate and Impact of Atmospheric Pollutants on Environmental and Human Health; McConnell, L., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013.

Publication Date (Web): November 8, 2013 | doi: 10.1021/bk-2013-1149.pr001

Preface Throughout the world, urban and agricultural communities have become more spatially intertwined resulting in blurred land use boundaries. Thousands of persistent and non-persistent organic pollutants are emitted to the atmosphere from primary and secondary sources. Emissions from urban, agricultural, and natural areas, such as particulate matter (PM10, PM2.5), volatile organic compounds (VOCs), and semi-volatile organic pollutants, can decrease overall air quality and negatively affect human health. These atmospheric pollutants can also be transported an deposited to proximate and remote ecosystems leading to adverse effects. After being emitted to the atmosphere, pollutants are subject to a variety of processes, such as diffusive air-water, air-soil and air-vegetation exchanges, gas-particle partitioning, dry/wet deposition, photochemical degradation, etc. All of these processes may influence their atmospheric occurrence, transport, deposition, and impact on the environment. This publication, developed after a symposium at the 2012 Society of Environmental Toxicology and Chemistry World Congress in Berlin Germany, examines emerging trends in research related to the role of the atmosphere in facilitating the global transport of pollutants and as an exposure pathway for humans and wildlife. Major topics include the examination of atmospheric processes controlling the fate and transport of persistent organic pollutants; modeling and assessment of human and wildlife exposure; and novel approaches for utilizing the atmosphere as a tool to assess sources of contamination. Transport processes controlling atmospheric transport and deposition of persistent organic pollutants (POPs) like air-water and air-soil exchange have been examined in numerous research publications. In the present work, Gioia et al. (Chapter 1) take a fresh look at recent findings in the cycling of PCBs and processes that control their transport from source regions to remote oceanic environments. High PCBs concentrations off the Western coast of Africa indicate new source regions in the Southern Hemisphere which has been relatively uncontaminated in the past. Cabrerizo et al. (Chapter 2) extend the discussion of POPs transport to include air-soil exchange and additional compound classes: polycyclic aromatic hydrocarbons (PAHs) and organochlorine pesticides. Their findings indicate that annual cycles of volatilization from soils in lower latitudes have become important secondary sources of POPs which are available for transport to cooler areas at higher latitudes. In recent years, scientists have also utilized their understanding of air-water and air-soil partitioning to make new discoveries regarding unknown global sources of POPs and other contaminants. Work by Bidleman et al. (Chapter 8) focuses on the question of whether there are sources of “new” DDT in North ix In Occurrence, Fate and Impact of Atmospheric Pollutants on Environmental and Human Health; McConnell, L., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013.

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America. Utilizing knowledge regarding the technical formulation components, the physical and molecular properties of the compounds, and archived samples from long term monitoring networks, this group has been able to distinguish a number of DDT sources to remote monitoring stations in the Arctic. Other contributors to this book have demonstrated the need for and the utility of large-scale atmospheric contaminant monitoring networks. Miglioranza et al. (Chapter 9) describe results of the Latin American Atmospheric Passive Sampling Network which utilizes XAD-2 resin samplers at over 50 sites in 12 countries. This long-term project is designed to generate critical information on sources and occurrence of POPs in South America and to examine the effectiveness of the Stockholm Convention at reducing overall concentrations of POPs in the Southern Hemisphere. In a region where monitoring networks are lacking, Castro-Jiminez et al. (Chapter 11) conducted a critical review of available over-water contaminant measurements in the Mediterranean Sea. PAHs were found to be the most abundant compound class of POPs entering the Sea from the atmosphere; however, the Mediterranean may also serve as a source of some compounds to the atmosphere in open sea regions where air concentrations are lower. Emissions of pesticides to the atmosphere from areas of heavy agricultural production has been a concern in many regions of the world. Research by Raina et al. (Chapter 10) has provided insights into changes in crop production and pesticide use in the Canadian Praries. Temporal variability in atmospheric pesticide concentrations were consistent with differences in weather and agricultural activity, and newly introduced pre-emergent herbicides were identified as having the potiential for long-range transport. In another agricultural region of North America, wetlands in California serving as habitat for amphibians were examined for agricultural pesticides and for correlations with population status in Fellers et al. (Chapter 7). Transects of sites from the Pacific coast to the Sierra Nevada Mountains were established to investigate potential exposure from atmospherically transported residues. Air pollution in the form of particulate matter has typically been associated with industrial processes and urban environments, but long range atmospheric transport of particulate matter from natural sources has become a concern from an environmental and human health perpective. Morman et al. (Chapter 3) have investigated the transport of particulate matter from dust storms in Mali, West Afica to areas downwind in the Cariibbean and measured trace metal concentrations. They also utilized in vitro bioaccessibility extraction methods to assess the potential for human exposure to Pb via inhalation and ingestion of particles collected at the source and at downwind sites. Results suggest that changes in trace metal bioaccessibility may be occurring during atmospheric transport and warranting further research. Delving further into the human exposure realm, Hertel et al. (Chapter 6) provide an overview of recent efforts in Denmark which combine air quality monitoring data with advanced spatial analysis tools and health registry data to examine human health risks associated with exposure to various urban air pollutants and to pollen. Results indicate that populations are exposed to regional sources and additional sources emitted within the city. Of particular concern are contributions from emission sources from less than 10 m above the ground such as those from high traffic areas. x In Occurrence, Fate and Impact of Atmospheric Pollutants on Environmental and Human Health; McConnell, L., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013.

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Of particular concern for human exposure is the presence of PAHs in ambient air. This class of compounds and their metabolites are known carcinogens, and exposure can occur in both urban and rural environments. van Drooge (Chapter 4) provides a critical review of recent findings regarding the fate of PAHs in different types of environments and examines the potential risks to human health from exposure to PAHs via the atmosphere. In addition, Fleming and Ashley (Chapter 5) explore the potential for humans who smoke tobacco to serve as vectors for PAH residues and reveal a previously unexplored exposure route (third-hand smoke) for non-smokers. Scientists contributing to this book cross the boundaries of environmental science, atmospheric chemistry, and toxicology. Increased interaction among scientists from different disciplines will be required achieve a greater understand of the role the atmosphere plays in transporting contaminants to remote regions and contributing to the exposure of humans and wildlife to a variety of pollutants.

Laura L. McConnell Research Chemist United States Department of Agriculture Agricultural Research Service Beltsville, Maryland 20705, USA

Jordi Dachs Department of Environmental Chemistry Institute for Environmental Assessment and Water Research (IDAEA-CSIC) Barcelona, Catalonia, 08034, Spain

Cathleen J. Hapeman Research Chemist United States Department of Agriculture Agricultural Research Service Beltsville, Maryland 20705, USA

xi In Occurrence, Fate and Impact of Atmospheric Pollutants on Environmental and Human Health; McConnell, L., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013.

Chapter 1

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Atmospheric Transport, Cycling and Dynamics of Polychlorinated Biphenyls (PCBs) from Source Regions to Remote Oceanic Areas Rosalinda Gioia,*,1,2 Jordi Dachs,2 Luca Nizzetto,3,4 Rainer Lohmann,5 and Kevin C. Jones6 1CSIC-IDAEA

C/Jordi Girona 18-26 08034, Catalunya, Spain for Environment, Fisheries and Aquaculture Science (Cefas), Pakefield Road, Lowestoft, NR33 0HT, UK 3Norwegian Institute for Water Research, Gaustadalléen 21, NO-0349, Oslo, Norway 4Research Centre for Toxic Compounds in the Environment (RECETOX), Kamenice 126/3, CZ-62500 Brno, Czech Republic 5Graduate School of Oceanography, University of Rhode Island, Narragansett, Rhode Island 02882-1197, USA 6Lancaster Environment Centre, Lancaster University, Lancaster LA1 4YQ, UK *E-mail: [email protected] 2Centre

Polychlorinated biphenyls (PCBs) are ubiquitous in the environment. Their persistence coupled with their potential toxicity has prompted international regulations and increased effort to understand their regional and global scale presence, and the processes that influence their fate and transport. PCBs can travel in the atmosphere away from source regions through long-range atmospheric transport and be deposited to water and terrestrial surfaces. This chapter focuses on the atmospheric concentrations of PCBs and factors controlling their spatial and temporal variability from source regions to oceanic remote areas. Air data show a strong latitudinal trend with the highest PCB concentrations in Europe and the lowest in the Arctic and in the tropical and subtropical southern hemisphere. High PCB levels were observed off the west coast of Africa and Asia, and possible factors controlling these high levels and

© 2013 American Chemical Society In Occurrence, Fate and Impact of Atmospheric Pollutants on Environmental and Human Health; McConnell, L., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013.

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their implications for the global cycling of PCBs are discussed. Furthermore, air-water interactions are disussed in remote areas of the open ocean. Of particular importance is the evidence for near steady-state air-water equilibrium or net volatilization in the tropical and subtropical regions, while advective inputs still dominate in the Northern hemisphere. Net deposition dominates over volatilization in the Arctic region. This chapter seeks o examine recent findings in the global transport of PCBs and to identify areas of uncertainty in the understanding of the factors controlling the residence time of PCBs in different areas of the globe.

Introduction PCBs were first synthesized in 1881 by Schmidt and Schulz but their commercial production only began in 1929 in USA (1). They were marked as mixed products under various trade names depending on the country where they were produced such as Aroclor (Monosanto, USA), Phenochlor and Clophen (Bayer, EU). Because of high chemical and thermal stability, electrical resistance, low or no flammability, PCBs had extensive applications. They have been used as dielectric fluids in capacitors and transformers, in plasticizers, adhesives, inks, sealants and surface coatings (2–4). Their basic structure is a biphenyl with one to ten chlorine substituents and a general structure of C12H10-nCln (n=1-10, m=1-10) (Figure 1).

Figure 1. Molecular structure of PCBs.

There are 209 different congeners with one to ten chlorines atoms attached. The International Council for the Exploration of the Seas (ICES) has reported that 7 PCB congeners are frequently reported reported in environmental samples are PCB 28 (2,4,4′-triPCB), PCB 52 (2,2′,5,5′-tetraCB), PCB 101 (2,2′,4,5,5′-pentaCB), PCB 118 (2,3′,4,4′,5-heptaCB), PCB 138 (2,2′,3,4,4′,5-heptaCB), PCB 153 (2,2′,4,4′,5,5′-heptaCB), PCB 180 (2,2′,3,4,4′,5,5′-heptaCB). The seven ICES PCBs were recommended for monitoring by the European Union Community Bureau of Reference; these PCBs were selected as indicators due to their relatively high concentrations in technical mixtures and their wide chlorination range (3–7 chlorine atoms per molecule).

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Production of PCBs peaked in the 1960s in Europe and USA and terminated in the mid 1970s, when they where ultimately banned in the late 1970s/early 1980s (3). The most recent inventory of PCB production estimates the cumulative global production of PCBs at 1.3 million tonnes (5). Approximately 97% of this has been used in the Northern Hemisphere, mostly between 30 °N and 60 °N (5). Before the ban, PCBs entered the environment through both point and diffusive sources such as landfill sites, accidental releases/spillages via leaking during commercial use of electrical equipment and transformer and capacitor fires, incineration of PCB waste (1, 3). Current atmospheric levels of PCBs in the environment are due to primary anthropogenic emissions (e.g. accidental release of products or materials containing PCBs), volatilization from environmental reservoirs which have previously received PCBs (e.g. oceans, large lakes and soil), incidental formation of some congeners during combustion processes (5) or PCB containing e-waste transported to developing countries (6–8) PCBs are also classified as persistent organic pollutants (POP) by the UN-ECE (United Nations Economic Commission for Europe) Convention on Long-Range Transboundary Air Pollution (CLRTAP), because they: a) possess toxic characteristics; b) are persistent in the environment; c) tend to bioaccumulate in higher trophic levels; d) undergo long-range atmospheric transport; and e) can result in adverse environmental and human health effects at locations near and far from sources. POPs represent a very small percentage of chemicals in commerce, and many of them are already strictly regulated or banned from production and use. Due to their persistence and their tendency to undergo long-range atmospheric transport, they have been detected in all the environmental compartments, even in remote areas like open ocean and polar regions, where POPs have never been manufactured or used (9–12). As a result, their regulation has become an international policy issue based upon their possible effects on human health and potential environmental risks (13). Atmospheric transport has been regarded as the main route for dispersing PCBs away from industrialized and densely populated areas and depositing to water and terrestrial surfaces (9, 14–16). Once in the environment they degrade only very slowly and recycle and partition between the major environmental media depending on their physical-chemical properties. Persistence is an important environmental concern since toxic effects do not dissipate significantly over time and their risk assessment is difficult (17). In addition, they have low aqueous but high lipid/organic solubilities which results in their bioaccumulation in lipid-rich tissues and in their biomagnification through food chains (18, 19). Equilibrium Partition coefficients such as the octanol-water (KOW) partition coefficient and the bioconcentration factor (BCF) refer to their hydrophobic and lipophilic nature and their tendency to bioaccumulate in the food-web. Conversely, the half-life gives insight into the time required for a contaminant to degrade in an environmental compartment. Partitioning is not just related to the properties of the chemical, it also depends on the conditions of the surrounding media, the presence of other reactive compounds or the mode of entry of the compound into the compartment (20).

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Primary and Secondary Sources In order to regulate and control the release of PCBs into the environment it is important to know how the chemical has been released. The fate and transport of PCBs are dependent on their physical-chemical properties and the geographical position and distribution of their sources. Generally, they are directly emitted into the environment from primary and diffusive sources, accidental releases and disposal. After they have been released, they can be trapped in environmental reservoir (e.g. soil and oceans) and volatilize from these back into the atmosphere (secondary sources). A major question is the extent to which current ambient levels are controlled by primary sources or re-emission/re-cycling of secondary sources (21–24). Figure 2 is a conceptual diagram, showing how ‘a primary source controlled world’ (scenario 1) compared with a ‘secondary source controlled world’ (scenario 2). In scenario 1, PCBs emissions would be continuing from diffusive primary sources in areas of past use (i.e. urban/industrial locations) and reaching background locations via LRAT/advection. Over long time intervals, site-by-site differences in the rates of PCBs loss would not be expected, provided primary emissions are dominating and they continue to emit the compound mixture over time (7). In scenario 2, however, site-by-site differences in rates of loss may be apparent, because the rates of re-emission and reaction would be dependent on air-surface characteristics and environmental variables (e.g. temperature).

Long-Range Atmospheric Transport The atmosphere is the major pathway for the delivery of PCBs to water and terrestrial surfaces; therefore, in this sense it represents a critical compartment for the global distribution and cycling of PCBs. As mentioned earlier, first emissions and then atmospheric long-range transport are major mechanisms to distribute PCBs widely through the global environment. Persistence and long-range atmospheric transport (LRAT) are two essential properties for defining POPs. First, in source regions the chemical must be emitted in the atmosphere in significant quantities either by primary or secondary emissions. Second, the chemical must be sufficiently persistent to be transported through the atmosphere to remote regions. The residence time gives an indication of the average life expectancy of a pollutant in an environmental compartment; indeed it is an indicator of persistence and is best calculated at steady state. Under unsteady-state or dynamic conditions, a characteristic time is often calculated similarly as the mass divided by the output rate. It is the average time that the chemical spends in the compartment. Half-life (t1/2) is defined as the time span within which the chemical decays by 50% of the initial concentration. 6 In Occurrence, Fate and Impact of Atmospheric Pollutants on Environmental and Human Health; McConnell, L., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013.

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Figure 2. Conceptual diagram of a ‘primary sources controlled world’ (scenario 1) and a ‘secondary sources controlled world’ (scenario 2). (adapted from Gioia et al. (23))

Spatial and long-term trends have been monitored by many multinational and national air sampling networks of selected POPs, such as the joint Canada-US, Integrated Atmospheric Deposition Network (IADN), the New Jersey Atmospheric Deposition Network (NJADN) in the US and the Toxic Organic Micro Pollutants Survey (TOMPS) in the UK, operated on behalf of the UK Department of the Environment, Food and Rural Affairs (DEFRA), or the European EMEP database from ground stations (http://www.nilu.no/projects/ccc/emepdata.html). Recently, studies that have used passive samplers (PAS), have been useful in our understanding of the spatial and temporal distribution of POPs (21–27). Many of these studies have shown that half-lives of PCBs are typically of 4-5 years (23, 24, 28–30). The IADN and EMEP monitoring networks have noted negative gradients of air concentrations away from the emission source that supports the findings of lower reported concentrations over the open-ocean than at the coast (6, 8, 30–33). Additionally, samples from North-South latitudinal transects in the Atlantic indicate higher concentrations in the Northern Hemisphere than in the Southern Hemisphere (6, 8, 30–37). This finding broadly reflects the ongoing emissions of PCBs. from populated/industrialized regions of the Northern Hemisphere . Finally, it should be noted again that monitoring networks in remote oceans are lacking. They are mostly found in land or coastal sites. However, long-term studies over the open ocean and other remote locations are scarce. Since they involve large financial costs and it is unrealistic to assume 7 In Occurrence, Fate and Impact of Atmospheric Pollutants on Environmental and Human Health; McConnell, L., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013.

that monitoring studies can cover the large number of POPs (and newly emerginf contaminants) and geographic areas that are needed to assess the risks posed by these chemicals to the overall ecosystem health.

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Condensation and Global Fractionation As mentioned earlier, PCBs have been found in pristine environments like the Arctic and the Antarctic regions (9–11, 33, 34). This behaviour was explained in the formulation of the “Global Fractionation” hypothesis, which has influenced both the regulatory and scientific communities. Because PCBs are semivolatile, they have the tendency to volatilise at higher ambient temperatures and be deposited as temperatures decline. Wania and Mackay (38) proposed the idea that POPs can potentially migrate from warmer regions and become fractionated on latitudinal and altitudinal gradients during LRAT on a regional and global scale. This concept embodies ideas about “Global Distillation”, “Cold Condensation”, (i.e. that compounds could become enriched in colder environments), and “Global Fractionation” (i.e. that the compound mixture changes with travel distance) (38). The extent of global fractionation will depend on the physical-chemical properties of compounds such as vapour pressure (PL) and octanol-air partitioning coefficients (KOA). PL describes the tendency for liquids and solids volatilize. KOA expresses the partitioning of a chemical to between air and organic matter (38), assuming that octanol is a good surrogate for organic matter. According to the global fractionation theory, the more volatile PCB congeners will be transported and condensed in colder regions and less volatile congeners will be deposited in warmer regions close to sources. The effect of this would be a relative enrichment of the more volatile compounds in colder (polar) areas over time. Two major scenarios can lead to global fractionation; 1) after being released by primary sources, a chemical is deposited near or far from sources depending on its physical chemical properties. In this case the environmental reservoir will act as a sink and absolute amounts will be expected to decrease with distance from sources areas (primary sources dominate); 2) re-emission from environmental reservoir will control the air concentration. In this case the fractionation will become more important over time and the concentration of some chemicals can increase with latitude (secondary sources dominate) (see Figure 2) Over the last 20 years there has been a significant interest in studying and testing these concepts (21–24, 33, 34). However, to summarize several studies, it is clear that many factors (other than temperature) also exert an influence over the regional and global scale distribution of PCBs. These includes: proximity to sources, properties of the receiving environment (e.g. soil organic matter contents; water body particulate and biological properties; atmospheric reaction rates) (39). Other factors that influence PCB transport are sinking particles in the water column, wet and dry deposition, degradation processes, burial in sediments, etc. Indeed, a range of biogeophysical variables not considered traditionally such as the phytoplankton biomass, the extent of the ocean Mixed Layer Depth (MDL), spatial and temporal differences in aerosol concentrations, ocean stratification, 8 In Occurrence, Fate and Impact of Atmospheric Pollutants on Environmental and Human Health; McConnell, L., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013.

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and the turbulent diffusion coefficient, could also play an important role in the fate of POPs in the oceans. Uncertainties remain whether environmental reservoirs act as sources or sinks and whether primary or secondary sources are controlling the levels of PCBs in the environment (22, 25, 40, 41). Gioia et al. (33) found decreasing concentrations at higher latitudes and evidence of fractionation processes with increasing concentrations of less chlorinated PCBs at high latitudes, which are less prone to cold trapping and being sequestered by organic matter in the ocean. Nevertheless, the cold condensation effect of substances at high latitudes is generally accepted, especially for terrestrial ecosystems. Therefore, POPs in the Northern polar environment is considered as “priority issue” by the Arctic Monitoring and Assessment Programme (42).

Deposition and Other Atmospheric Removal Processes The oceans play an important role in controlling the environmental transport, fate and sinks of POPs at regional and global scales (38, 43). Although PCB concentrations in the open ocean have been shown to be lower than those observed in coastal areas (9, 10, 44) the large oceanic volume implies that they may represent an important inventory of PCBs. Furthermore, the pathway air – deposition – water – phytoplankton – food web transfer – wildlife/human exposure is of key importance for these bioaccumulating compounds. Many studies including modelling work have shown that terrestrial organic matter (soil and forested surfaces) has an important influence on the dynamics and inventory of POPs (45–47). Therefore, it is logical to think that high productivity regions of the ocean may exert an important influence on the global distribution of PCBs. Jurado et al. (39), assessed the spatial and seasonal variability of the maximum reservoir capacity of the ocean compartment to act as a sink of PCBs and showed that temperature, phytoplankton biomass and mixed layer depth (MLD) can influence the reservoir capacity of the ocean (i.e. air-ocean equilibrium/storage issues). However, kinetically controlled processes such as particle settling, reactions and metabolism also need to be considered. In the water column, PCBs can be found truly-dissolved, sorbed to colloids or sorbed to particles. Hydrodynamics of the water masses, such as turbulence and marine currents, influence the spatial distribution of PCBs in the ocean (48). Dissolved PCBs can volatilize back to the atmosphere or can sorb to particles and organisms such as phytoplankton, and they can be removed from the surface waters and delivered to the deep ocean by sinking of particles and by zooplankton vertical migration. This will depend on the physical-chemical properties of the congeners. The Henry’s Law constant (HLC) is the ratio between the compound saturated liquid vapour pressure and its solubility in water. Therefore, a compound with higher KOW and lower HLC will tend to partition to particles in the water column and sink to the deep ocean, while those with lower KOW and higher HLC values will volatilise back to the atmosphere more easily. Depending on several environmental factors, the oceans can act as a source of PCBs to the atmosphere, as a storage compartment or as a sink. However, there is a lack of open ocean 9 In Occurrence, Fate and Impact of Atmospheric Pollutants on Environmental and Human Health; McConnell, L., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013.

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seawater data due to the difficulties associated with the sampling procedures for PCBs (e.g. large volume, partition to colloids, etc), shipboard and laboratory contamination and the costs associated with the use of ships in the open ocean. In the atmosphere, PCBs partition between gas and aerosol phases and may then be removed by five major mechanisms: dry deposition of particle bound pollutants, diffusive gas exchange between the atmosphere and the surface ocean, scavenging by precipitation (wet deposition) and OH˙radical degradation. Figure 3 is a conceptual diagram of the major processes affecting PCBs in the oceanic atmosphere. Many studies have acknowledged the importance of air-water exchange in understanding the environmental fate of PCBs at local, regional and global scales (39, 49–52). Gaseous exchange of contaminants between the atmosphere and the ocean is driven by a concentration difference and transport by molecular and turbulent motion. Knowledge of whether surface ocean waters/lakes are in dynamic equilibrium with the atmosphere, or the net direction of flux (i.e. whether absorption or volatilization dominates), is therefore crucial for our understanding of the global cycling and fate of PCBs. Air-water exchange is the most dominant depositional process at the global scale compared to wet and dry deposition (39). Available measurements of PCB air-water exchange fluxes in remote oceanic regions are very scarce because of the lack of simultaneous measurements of air and seawater, even though they are needed because of the key role of oceanic controls on regional and global dynamics and sinks of these chemicals.

Figure 3. Major processes affecting POPs in the atmosphere and the ocean. (from Gioia et al. (53)) 10 In Occurrence, Fate and Impact of Atmospheric Pollutants on Environmental and Human Health; McConnell, L., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013.

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Jurado et al. (54) estimated that wet deposition shows a high spatial and seasonal variability, with maxima located in the Intertropical Convergence Zone (ITCZ) and in low temperature regions. Seasonal variability reflects the northward shift of the ITCZ in the Northern Hemisphere in July. Average wet deposition fluxes estimated for the Atlantic Ocean in this study are 110 ng m-2 yr-1. However, when raining events and non-raining time periods are integrated, air-water diffusive exchange fluxes acquire an important role, which can be dominant in some regions and for some POPs. The contribution of dry depositional fluxes to total deposition has been estimated by Jurado et al. (39) over the Atlantic Ocean. The results of the study show that for all the PCB congeners, air-water exchange dominates the dry deposition mechanisms with the exception of mid-high latitude where low temperature and high wind speed can enhance dry depositional fluxes for the less volatile PCB congeners. Anderson and Hites (55) suggest that reactions with OH-radicals are the major removal pathway for PCBs in the atmosphere. Mandalakis et al. (56) showed that gas phase concentrations of PCBs were depleted significantly due to the oxidative attack of OH radicals at remote sites of Eastern Mediterranean. However, other studies have shown diurnal cycles over the pristine ocean atmosphere57, with daytime concentrations higher than night time, suggesting that other processes, not just atmospheric reactions, play a role. Jaward et al. (57) suggested that there were a number of water column biogeophysical processes controlling the gas phase concentrations in the atmospheric boundary layer. This raises important questions about air-water exchange and within-ocean processing of POPs.

Equilibrium Partitioning Partition coefficients have been widely used to describe the distribution and partitioning of PCBs into the environment. The concept of partition coefficients indicates equilibration between two phases due to diffusion. When there is no net transfer of mass of chemical between the phases and the concentrations of chemical in each phase is constant equilibrium is reached, and the resulting ratio is called the equilibrium partition coefficient. In the real world there are many situations where equilibrium partitioning is not reached. However, these coefficients are useful to characterize how long it would take for a compartment to reach equilibrium or to determine the tendency of a chemical to accumulate in one compartment. On the other hand, equilibrium partition constants are needed to calculate the rate of transfer of a compound across interfaces, as shown earlier. From an environmental standpoint, the HLC is a key parameter used to model the diffusive exchange of semivolatile chemicals such as PCBs between surface waters and the atmosphere (49, 50, 58, 59). Accurate knowledge of a chemical’s HLC and how it changes with environmental conditions, including temperature and ionic strength, is essential to predict the environmental behaviour, transport, and fate of many classes of organic chemicals. HLC has been determined in laboratory studies using different methodologies and its determination is subject to a heated debate (60, 61). Furthermore, various sensitivity studies have noted that HLC can constitute an important source of 11 In Occurrence, Fate and Impact of Atmospheric Pollutants on Environmental and Human Health; McConnell, L., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013.

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uncertainty in the estimation of the net direction of the fluxes (62). Laboratory experimental determinations of HLC are performed with pure water, while natural waters contain varying levels of DOC, colloids, suspended particles and salts. These constituents can modify the partitioning of hydrophobic compounds into the dissolved phase and in turn the HLC. However, there is little systematic understanding of the role of these factors. Gioia et al. (53) estimated field-derived air-water partition values for PCBs and found that they were a factor of 2-3 higher than those reported previously from standard measurement procedures made in the laboratory using pure water and much higher PCBs concentrations. It is interesting to speculate that if the field data give the ‘right’ values for HLC, there are important implications for how laboratory measurements are made and used in PCBs modelling. This highlights that significance of non-ideal solutions in environmental systems will need to receive more research attention in the future, since it could influence not only laboratory determination of Henry’s Law constants, but the determination of other physical-chemical properties.

Temporal Trends of PCBs On average PCBs are declining in the atmosphere of Europe and North America, typically with an average half life of 4–5 years (23, 24, 28). In the Arctic atmosphere, temporal trends comparisons with earlier measurements from the NCP and the AMAP datasets shows that PCBs are slowly declining in the European Arctic atmosphere (33, 34). In contrast, little change is observed in air concentrations over the remote open ocean over the past 19 years (1990-2009) (6, 8, 32, 37). Of particular importance is also the evidence in this study for close air-water coupling in the southern hemisphere (i.e. close to steady state conditions), while advective inputs still dominate in the northern hemisphere (6, 32). If a half life of 4–5 years is assumed to also apply to the open Atlantic Ocean, the concentration between the 1990 and 2005 should differ by about a factor of 8–10 –presumably sufficiently different to be detectable. The lack of a measured difference perhaps implies that air concentrations in these remote oceanic environments are undergoing little change, compared to the declines observed at the land-based locations close to sources. Interestingly, Panshin and Hites (63) compared PCB in oceanic air over Bermuda in 1992/1993 with those of several studies in 1970s at the same location, and found no statistically significant difference. Hillery et al. (29) also concluded that the atmospheric concentrations of PCBs near Lake Superior, the most remote of the Great Lakes, remained unchanged over a period of 6 years. Axelman and Broman (64) argued that these observations indicate PCBs may be removed slowly from the environment, when viewed from a global or hemispheric perspective, with PCBs being diluted into the remote areas of the earth rather than being permanently removed from global cycling. This implies that source-region gradients would decline over time as PCBs become more uniformly distributed (65). The comparison of results with those of land-based and other oceanic studies 12 In Occurrence, Fate and Impact of Atmospheric Pollutants on Environmental and Human Health; McConnell, L., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013.

should give insights into changing levels and distributions of organichlorine pesticides (OCPs) and PCBs over the different geographical regions. This comparison must be done cautiously, because they only reflect short sampling periods and therefore specific conditions such as atmospheric circulation and also the exact route of the sampling vessel and different sampling techniques which influence sampling in the ocean.

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Spatial Trends Source inventories of PCBs show that the ratio of emissions between the northern and the southern hemisphere (NH:SH) is ~20:1. However, ambient levels show a smaller difference. Inaccuracies with the source inventories and/or NH “dilution” to the SH over time may explain these observations. Relatively high levels of PCBs have been reported for the West African coast during different cruises on board two different vessels, RV Pelagia and RV Polarstern, in 2001, 2005 and 2007 respectively (6, 8, 25, 26). The sources were unknown although strong land-based emissions are suspected. Source inventories have not identified Africa as important for PCB usage raising interesting questions about unaccounted for sources/processes. A strong latitudinal trend over the oceans is also observed within the Northern hemisphere with the highest PCB concentrations near the coasts of Europe, North America and Asia and the lowest in the Arctic and tropical and subtropical remote regions of the Pacific, the Atlantic and the Indian ocean, suggesting that the underlying levels in the remote marine atmosphere are controlled by LRAT (32–34, 36, 37). Gas-phase concentrations have also been reported to increase near the icemargin zone, presumably due to enhanced volatilization induced by ice melting, which could be currently enhanced due to climate change (33, 34). Gioia et al. (33) raises questions about the role of ice as a compartment/buffer/source/sink for POPs in the Arctic, both in the short-term and as global climate changes occur to affect the properties and the extent of the ice sheets. Zhang et al. (36) reported PCB concentrations in the remote Pacific ocean and found that, in general, average NH air concentrations were about 4 times higher than in the SH. The range of atmospheric ΣICESPCBs reported is similar to measurements by Jaward et al. (25) (4.5-120 pgm-3) and Gioia et al. (32, 33) (3.7-220 pg m-3) for the Atlantic and the Arctic Ocean (0.8-100 pg m-3). In a more recent study on a cruise East to West cruise transect, from Shanghai, China to Cape Verde in the Central Atlantic Ocean, Gioia et al. (8) reported the mean concentration of Σ7PCBs in the present study is in the same range as those measured in European background sites (2-121 pg m-3) (66). Breivik et al. (7) reported that potential sources in the African and Asian regions of relatively high levels of PCBs may include illegal dumping of PCB-containing wastes with release via volatilization and uncontrolled burning, and the storage and breakup of old ships. Therefore, emissions of some industrial organic contaminants may be decreasing faster in former use regions (due to emission reductions combined with uncontrolled export), at the expense of regions receiving these substances as obsolete products and wastes. 13 In Occurrence, Fate and Impact of Atmospheric Pollutants on Environmental and Human Health; McConnell, L., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013.

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Air-Water Exchange of PCBs and Oceanic Sinks Gaseous exchange of contaminants between the atmosphere and the ocean is driven by a concentration difference and transport by molecular and turbulent motion. Air–water gas exchange is the most dominant depositional process at the global scale compared to wet and dry deposition (39) for those PCBs which atmospheric occurrence is mainly in the gas phase. In general, Gioia et al. (33) reported a net deposition of PCBs in the Arctic region especially near the marginal ice zone due to an increase in atmospheric concentrations of PCBs, but there were uncertainties whether the ice was a source of POPs to the atmosphere or whether it is due to ice-water-atmosphere interactions. Knowledge of contaminant levels in sea ice remains one of the weakest and more controversial areas of the Arctic research. The biological pump plays also an important role by removing PCBs from the water column, modifying the air–water gradient in concentrations which leads to enhanced net deposition of PCBs. Dachs et al. (43) assessed the role of the biological pump at the global scale. They reached the conclusion that increased atmospheric deposition fluxes were found at high latitudes and in other regions with high primary productivity such as upwelling regions. Jurado and Dachs (67) have also shown that the biological pump can considerably reduce the atmospheric residence times of hydrophobic PCBs by sequestering PCBs from the atmosphere. Malagón-Galbán et al. (34) provided the first field evidence of the role that the biological pump plays in productive oceanic Arctic regions, and confirms that the biological pump reduces and minimizes the transport of PCBs to the Arctic during the summer. Several studies have shown that air and water concentrations of PCBs are close to equilibrium conditions in more oligotrophic areas of the tropical and subtropical regions of the remote ocean because of the lack of the biological pump (24, 32). More recent studies have reported net volatilization of PCBs in subtropical and tropical regions of the Pacific, Atlantic and Indian Oceans (8, 36, 37). Zhang et al. (36) suggested that ceased production and usage of PCBs as well as degradation have led to lower environmental concentrations. The relatively low atmospheric concentrations combined with the relatively low sinking of particulate matter can result in a reduced air-water gradient and an increase in net volatilization. What is clear is that increased net deposition occurs in high productivity areas like the Arctic regions, while net volatilization is observed in the tropican and subtropical regions of the oceans. What is unclear from the present and previous studies (8, 36, 37) is whether the revolatilization observed in the subtropical ocean is due to a temporary or to a permanent condition of the ocean and to what extent potential new sources of PCBs (6–8) in Asia and Africa for example can eventually affect the reservoir capacity of POPs in the remote or adjacent ocean.

Conclusions Primary emissions and then LRAT are major mechanisms to distribute PCBs widely through the global environment. Once in the atmosphere they can be distributed in the pristine remote oceanic environment far from sources and trapped in cold regions such as the Arctic. Generally, higher atmospheric PCBs 14 In Occurrence, Fate and Impact of Atmospheric Pollutants on Environmental and Human Health; McConnell, L., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013.

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concentrations are measured in the northern hemisphere than in the southern hemisphere, which is in agreement with historical global production. Sources inventories show that the ratio of emissions between the northern and the southern hemisphere (NH:SH) is ~20:1. Inaccuracies with the source inventories and/or NH ‘dilution’ to the SH over time may explain these observations. High PCB levels found off the west coast of Africa and Asia raise interesting questions about unaccounted for sources/processes. A strong latitudinal trend over the oceans, with the highest PCB concentrations in Europe and the lowest in the Arctic and the remote tropic and subtropical ocean, suggests that the underlying levels in the remote atmosphere are controlled by LRAT, with deposition dominating over volatilization for PCBs. Air-water exchange has been regarded as the most important depositional process of PCBs to the ocean waters. The direction of the air-water fluxes give insight on the role of ocean as source or sink of PCBs. There is the evidence for near steady-state conditions or net volatilization in the southern hemisphere, while net deposition still dominate ambient levels in the northern hemisphere including the Arctic region. This raises questions about the role of ice as a compartment/ buffer/ source/ sink for POPs in the Arctic, both in the short-term and as global climate changes occur to affect the properties and the extent of the ice sheets.

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Chapter 2

Soil-Air Exchange Controls on Background Atmospheric Concentrations of Polychlorinated Biphenyls (PCBs), Organochlorine Pesticides (OCPs), and Polycyclic Aromatic Hydrocarbons (PAHs): A Case Study from Temperate Regions Ana Cabrerizo,† Jordi Dachs,* and Damià Barceló Department of Environmental Chemistry, IDAEA-CSIC, Jordi Girona 18-26, Barcelona, Catalonia, 08034, Spain *E-mail: [email protected] †Current Address: European Commission Joint Research Centre, Institute of Environment and Sustainability, Via Enrico Fermi 2749, I-21027 Ispra, VA, Italy

The environmental fate of persistent organic pollutants (POPs) depends on their behavior and transport at local and global scale, and soil-air exchanges processes are believed to play a major role controlling POPs reservoirs and global distribution. Measurements of POPs fugacity gradients suggest that soils from lower latitudes and temperate regions, as those studied in the Ebro river watershed (Spain), are starting to be important secondary sources of polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) to the atmosphere and that atmospheric background concentrations of PCBs, OCPs and polycyclic aromatic hydrocarbons (PAHs) are now controlled by temperature dependent re-emissions from soils. In contrast, regions where the soil-air partition coefficient (KSA) values are elevated due to higher soil organic matter content (SOM) or lower temperatures, as is the case of UK sampling sites, soils will act as important traps and accumulate more PCBs and OCPs. These regions will need more time to reach equilibrium and become significant secondary sources. The close coupling of POPs fugacities in soil and air suggest a strong control of

© 2013 American Chemical Society In Occurrence, Fate and Impact of Atmospheric Pollutants on Environmental and Human Health; McConnell, L., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013.

the atmospheric occurrence of POPs in the lower atmosphere in rural regions.

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Introduction Over the last 50 years and due to the economic development, humans have manufactured and consumed thousands of synthetic chemicals in industry and agriculture, some of them classified as persistent organic pollutants (POPs), such as polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) (e.g dichlorodiphenyltrichloroetane (DDTs), hexachlorocyclohexane (HCHs) or hexachlorobenzene (HCB). As a result, some environmental compartments, such as soils, have become important reservoirs of POPs (1), with a historical net accumulation of POPs while primary emissions were important. In background regions with no historical direct inputs to soils, the occurrence of these chemicals in the atmosphere and soils is influenced by their volatilization from soils and atmospheric deposition events as the main vector for their spatial re-distribution from secondary and potential primary regional sources. In addition to man-made POPs, the presence of polycyclic aromatic hydrocarbons (PAHs) in soils has received much attention since the 60’s (2). Combustion of fossil fuels, such as coal and petroleum in domestic and industrial applications, and biomass combustion are the major anthropogenic sources of PAHs to the environment. In addition to combustion processes, there is some evidence for biogenic PAH formation in the environment (3–6). Soil-air partitioning is a key process driving the environmental fate of POPs and PAHs in the environment, and determining the extent of soils as a reservoir of organic pollutants. Indeed, due to POP’s physico-chemical properties, especially their strong affinity with soil organic matter (SOM), soils have become the largest terrestrial reservoirs for POPs (7). Due to POPs partitioning with SOM, the availability of POPs to undergo biological degradation, remobilization, burial and toxic effect have been suggested to be linked to the carbon cycle thus suggesting that POPs are part and are interrelated with the carbon cycle (8). Beside the soil properties, the flux and direction of air-soil exchange of POPs have been reported to be influenced by climatic factors and also chemical emission (9–13). It is clear that primary sources dictated levels in the past, especially during the initial period of increasing production, use, and emissions. However, as restricted measured in the use of PCBs and OCPs were adopted decades ago, it is believe that secondary sources will dominate the future presence of these chemicals in the atmosphere. Despite the great interest that the soil-air exchange of POPs between the atmosphere and the soil has raised over the last years, soil fugacity is usually estimated from models of the soil-air partition coefficient (KSA) with the associated unavoidable uncertainties associated with these parameterizations (14, 15). The pioneering work from Hippelein and McLachlan (16) allowed to determine the fugacity in soil in laboratory conditions by stripping soil with air, showing than both temperature and humidity were important parameters affecting the soil fugacity. However, it is difficult to extrapolate these determinations of fugacity in soil to field conditions. The few previous attempts to measure soil-air 20 In Occurrence, Fate and Impact of Atmospheric Pollutants on Environmental and Human Health; McConnell, L., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013.

Publication Date (Web): November 8, 2013 | doi: 10.1021/bk-2013-1149.ch002

partitioning and fluxes in field conditions are the studies performed by Jones, Bidleman and co-workers (17–19). While they were appropriated to measured fluxes and gradients providing the concurrent meteorological parameters, it is not clear that the air-soil partitioning can be assessed because the gas phase concentration determined close to the soil may not have been equilibrated with the soil surface. The development and application of an operational soil fugacity sampler (20) opened the door, for first time, to field studies that accurately determine the variables driving the soil-air partitioning and fluxes of POPs in the field. Thus, the objectives of this chapter are to synthesize the work performed during several sampling campaigns using the soil fugacity sampler (20) in N-NE Spain and NW England with the aim i) to elucidate to which extent current atmospheric levels of PCBs, HCB, HCH and PAHs are controlled by volatilization from soils, and ii) provide a direct comparison of the different families of organic pollutants.

Experimental Approach Case Studies of PCBs, OCPs and PAHs in Background Soils of Temperate Areas Nine background sites in temperate areas of Northern Spain (along the Ebro river watershed) and Northwest UK were selected for the study of the influence of soil-air partitioning and exchange on the atmospheric occurrence of POPs (Figure 1). In total, four sampling campaigns were performed and distributed as followed: three sampling campaigns were carried out in June 2006, November 2006, and September 2007 in locations along the Ebro river basin (Spain), while the sampling in the UK sites was performed during August-September 2008. All the selected sites were non-agricultural rural or semirural sites with no direct sources of pollutants, so we assumed that all pollutants found there may have introduced by diffuse atmospheric processes. In order to measure the soil-air partition coefficient (KSA) under field conditions, soil surface samples at each sampling site were taken by gently collecting the soil surface layer (approximately top 0.5-1 cm) and analyzed for POPs concentration after sampling the air equilibrated with the soil. KSA describes the equilibrium partitioning of a chemical between the air and the soil and was calculated as follows:

where CS is the POPs concentration in the soil surface (ng g dw-1) and CSA (ng m-3) is the gas phase concentration that has been equilibrated with the soil surface. The air equilibrated with the soil surface was sampled by deploying the soil fugacity sampler (20) above the surface soil at each sampling site. Briefly, in this sampler, the air that has been equilibrated in terms of POPs fugacity with the soil surface passes through a glass fiber filter to remove dust particles and a polyurethane foam plug, in which the compounds from the gas phase were retained. Basically, the main advantage of this sampler in comparison to high volume samplers, is that allows for accurately determining the air equilibrated with the soil (thereafter defined as POPs fugacity in soil) by reducing the flow rate (8-10 l min-1) and thus 21 In Occurrence, Fate and Impact of Atmospheric Pollutants on Environmental and Human Health; McConnell, L., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013.

Publication Date (Web): November 8, 2013 | doi: 10.1021/bk-2013-1149.ch002

allowing for air that passes below the sampler to equilibrate in terms of POPs concentrations with the soil surface. The POPs fugacity in soil (fs) (in Pa) was therefore directly determined directly under field conditions by:

where R is the gas constant (8.314 Pa m3 mol-1 K-1), MW is the chemical molecular weight (g mol-1), and T is the temperature (K). Each sample was an integration of 24 h of sampling with a total air volume of 10-14 m3. In parallel to the soil fugacity sampler, an ambient air sampler located at 1.5 m height was also deployed operating with the same flow rate/conditions than the soil fugacity sampler in order to determine ambient air concentrations of POPs or ambient air fugacities (fa) (in Pa):

where Ca is the measured ambient air concentration in ng m-3.

Figure 1. Map of selected sampling sites along the Ebro river basin (Spain) and in NW UK 22 In Occurrence, Fate and Impact of Atmospheric Pollutants on Environmental and Human Health; McConnell, L., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013.

Publication Date (Web): November 8, 2013 | doi: 10.1021/bk-2013-1149.ch002

Analytical Methodology Briefly, soil samples and samples used to determine soil and ambient air fugacities were soxhlet extracted for 24 h in dichlorometane:methanol (2:1v/v) and acetone:hexane (3:1v/v) respectively and spiked with PCB 65, PCBs 200, phenanthrene-d10, crysene-d12 and perylene-d12. Extracts were then cleaned and fractionated using 3 g and 1.5 g alumina deactivated 3% respectively. Soil extracts were eluted in a first fraction (containing PCBs and OCPs) with 5 ml of hexane and with 12 ml dichlorometane: hexane (2:1 v/v) for the PAHs fraction. PCBs, OCPs and PAHs from soil and ambient air fugacity extracts were eluted in one single fraction using 12 ml dichloromethane:hexane (2:1 v/v). All samples were analyzed for the following PCB congeners, OCPs and PAHs: tri-PCB 18, 17, 31, 28, 33; tetra-PCB 52, 49, 44, 74, 70; penta-PCB 95, 99/101, 87, 118; hexa-PCB 110, 151, 149, 153, 132/105, 138, 158, 128, 169; hepta-PCB 187, 183, 177, 171/156, 180, 191, 170; octa-PCB 201/199, 195, 194, 205; nona-PCB 206, 208, 209. Regarding OCPs, the following compounds were analyzed: HCB, HCH isomers (α-HCH, β-HCH, γ-HCH, δ-HCH) and DDT and its metabolites (p,p′-DDT, o,p′-DDT, p,p′-DDD, o,p′-DDD, p,p′-DDE, o,p′-DDE) and for PAHs the following parent PAHs and alkyl homologues were analysed: phenanthrene (Phe), anthracene (Ant), fluoranthrene (Flu), pyrene (Pyr), benzo(a)anthracene (B(a)ant), chrysene (Cry), benzo(b&k)fluoranthene (B(b&k)f), benzo(e)pyrene (B(e)pyr), benzo(a)pyrene (B(a)pyr), perylene (Pery), dibenzo(a,h)anthracene (Dib(a,h)ant), benzo(g,h,i)perylene (B(g,h,i)pery), indeno(1,2,3-cd)pyrene (In(1,2,3-cd)pyr, dibenzonthiophene (DBT), methyldibenzonthiophenes (ΣMDBT), methylphenanthrenes (ΣMP), dimethylphenanthrenes (ΣDMPD). Quality assurance and control parameters have been provided elsewhere (6, 12, 13). The detected compounds in blanks were PCB 52, 70, 118, 149, 152, δ-HCH, p,p′-DDE, p,p′-DDT, Phe, Ant, Flu and their abundance were in the range of 2-10% of the levels found in samples, thus indicating minimum contamination during storage, sampling, transport and processing. Therefore, samples were not blank corrected. A gas chromatograph equipped with an electron detector capture (GC/EDC) (Agilent Technologies, model 6890N and 7890N) were used for PCBs and OCPs analysis using the method described elsewhere (12, 13). The quantitative analyses for PAHs were carried out by gas chromatography coupled to mass spectrometry (GC/MS). Samples were injected in an Agilent 6890 Series GC System coupled with a 30 m capillary column (HP-5MS, 0.25mm x 0.25um film thickness) (see method in Cabrerizo et al. (6)).

Results and Discussion Parameters Affecting Ambient Air Concentration (and Ambient Air Fugacities) Temperature (T) was observed to be the most important parameter influencing the atmospheric concentration of PCBs, PAHs and OCPs in temperate regions, with higher concentrations during the warmer sampling periods (June 2006 and 23 In Occurrence, Fate and Impact of Atmospheric Pollutants on Environmental and Human Health; McConnell, L., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013.

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September 2007). The influence of temperature is usually viewed as evidence that local or proximate sources, either primary or secondary, have a strong influence on the atmospheric levels of organic pollutants (21). This is consistent with the fugacity gradients observed, since they had a volatilization component for all chemical families (6, 12, 13). Figure 2 shows the influence of T on atmospheric concentrations for the POPs families studied. Overall, we observed that ambient air temperature affected ambient air concentrations of PCBs and OCPs, which higher concentrations in warm periods, in agreement with an enhance released of POPs from soils during warm seasons. This temperature influence on ambient concentrations was not observed for PAHs (e.g. phenanthrene and anthracene), which show a lack of dependence on temperature (e.g phenanthrene) or higher ambient air concentrations at lower temperatures (e.g anthracene). Different reasons may account for this behavior, i) the fact that PAHs are not persistent, especially in the atmosphere, with atmospheric half lives of hours due to reaction with OH radical. These degradation processes are more effective during warm periods, ii) the presence of higher emissions of PAHs due to heating, wood burning or other combustion sources during winter time, iii) the presence of potential biogenic sources in soils and other environmental compartments that may not be temperature dependent (6, 22). The lack of an influence of T for PAHs cannot be viewed as a sign of lack of local sources, but of varying sources at different seasons (biogenic and pyrolitic sources) and different extend of atmospheric degradation processes. Other studies have also reported a weak or lack of T dependence of atmospheric concentrations of PAHs (23), while the key role of temperature as a control of atmospheric concentrations of PCBs and OCPs has been described in numerous studies (21, 24, 25). If local sources control the atmospheric occurrence of POPs and PAHs in rural areas, it is important an assessment of the factors driving the air-soil partitioning and exchange of POPs.

Parameters Affecting the POPs Concentration and Fugacity in Soils Soil Properties The nature of the surface matrices in direct contact with the atmosphere are very important for the partitioning of POPs between the air and soil surfaces. This is particularly true if these surfaces are covered by lipophilic organic substances which offer a high capacity to store POPs. Soils contain these kinds of substances such as humic acids, which are able to retain POPs due to the high affinity of these pollutants to non-polar phases. Soil organic matter quantity is generally considered as the main descriptor of the sorption of hydrophobic pollutants (26) and has been recognized as an important variable that influences the concentration of POPs at local, regional and global scale (1, 27). Soils having the higher soil organic matter content in these studies have shown higher concentrations of all the chemicals considered: PCBs, OCPs and PAHs (Figure 3). This trend has been observed previously in other studies (1, 27) thus soil organic matter is a major reservoir of POPs at regional and global scales (1, 7) and its capacity to immobilize 24 In Occurrence, Fate and Impact of Atmospheric Pollutants on Environmental and Human Health; McConnell, L., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013.

Publication Date (Web): November 8, 2013 | doi: 10.1021/bk-2013-1149.ch002

POPs, preventing them from re-volatilization back into the atmosphere, was also evidenced for banned PCBs, α-HCH, γ-HCH and o,p′-DDT and p,p′-DDT metabolites as their soil fugacities (fs) are lower for those soils having the highest SOM content (Figure 4). This scenario contrast with the observation of PAHs and HCB fugacity in soil for which high variability was observed and it is not possible to elucidate significant differences due to soil organic matter content. In the case of phenanthrene, and consistent with the discussion done above on its potential biogenic sources, the lack of trend observed would be consistent with phenanthrene and methyl-phenanthrenes originating from degradation of organic matter (triterpenes), which would lead a higher fugacity at higher SOM content, but this trend could be masked by the role that higher SOM has as increasing the soil fugacity capacity, thus decreasing the tendency to escape from soil (fugacity). The common role of organic matter content as a descriptor of the burden of hydrophobic pollutants, and in agreement with previous studies in European soils (28), were observed between the different POPs families’ concentrations for ΣPCBs, ΣPAHs, HCB, ΣHCH and ΣDDT, across the whole set of soils (Figure 3). The common role of soil organic matter as a sorbing phase, induce that the concentrations of the different families of POPs are correlated among them with statistically significant correlation (p-level